Printing and coating compositions



United States Patent 3,375,120 PRINTING AND COATING COMPOSITIONS Robert K. Remer, 1500 Central St., Evanston, Ill. 60201 No Drawing. Original application July 17, 1961, Ser. No. 124,329, new Patent No. 3,303,160, dated Feb. 7, 1967. Divided and this application Aug. 4, 1966, Ser. No.

1 Claim. Cl. 106-27) ABSTRACT OF THE DISCLOSURE This application is a division of my copending application Ser. No. 124,329, filed July 17, 1961, now Patent No. 3,303,160, which was a continuation-in-part of my application Ser. No. 846,750, filed Oct. 15, 1959, now Patent No. 3,067,056, which was a continuation-in-part of my abandoned application Ser. No. 624,385, filed Nov. 26, 1956, which was a continuation-in-part of my original application Ser. No. 367,206, filed July 10, 1953.

My invention relates to improvements and innovations in compositions for use in printing and coating. More particularly, it relates to such compositions for use in practicing the process and using the apparatus disclosed in my Patent No. 3,067,056.

According to my prior application an ink or coating composition is dissolved in a volatile solvent which is retained in the lower portion of a tank or in a fountain. Means are provided in the bottom of the tank or fountain for controlling the temperature of the bath or solvent at approximately the boiling point thereof. An etched or mechanically knurled printing cylinder is mounted in the tank or fountain so as to run in the bath at the proper depth. The web or sheet material being treated is passed through the intaglio or rotogravure printing or coating unit located in the lower part of the fountain and thereby receives a metered surface deposit of the ink or coating in the form of tiny dots characteristic of intaglio or rotogravure printing. Since the temperature is maintained at or near the boiling point in the vicinity of the applicating cylinder, the volatile solvent is immediately vaporized, leaving behind a metered deposit of the ink or coating composition on the surface of the web in which the dots have become merged or joined into a continuous film on the surface. The upper portion of the tank or fountain extends above the printing or coating unit so as to retain the vapors therein and is provided with condensing means for condensing the solvent vapors so as to recover the same and prevent them from leaving the fountain. The web or sheet leaves the top of the tank in a substantially dry, solvent-free condition.

It has been found that this particular printing or coating process is practical when the ink or coating composition is applied from a rotogravure or intaglio type cylinder which will usually be over-all etched or mechanically knurled. Because of the type of deposit laid down on the web from such a cylinder in the form of multitudinous fine dots, it is possible to flash off and recover practically all of the chlorinated solvent used as the vehicle. When the web being printed is a fibrous or absorptive material such as paper, the chlorinated solvent still vaporizes from the tiny dots before it becomes absorbed or picked up by 3,375,120 Patented Mar. 26, 1968 the web. The deposit or coating which is: applied by an. etched or rotogravure cylinder is; very uniform and by selecting the depth and screen size of the etching or' knurling, the amount of the deposit or coating can be very closely controlled and accurately metered. The web being printed or coated travels at a fast speed which makes the process practical and economical without requiring large and expensive drying equipment and tunnels such as commonly are used in connection with rotogravure printing employing expensive volatile solvents.

An important object of my invention is the provision of printing and coating compositions particularly suited for use in practicing the process and using the apparatus disclosed in my Patent No. 3,067,056.

Another object of the invention are new and improved compositions for use in printing on smooth synthetic fihn such as polyethylene, polypropylene, polyvinyl and polyester films.

Another object of my invention are printing and coating compositions for the class described which have a high content of nylon scrap or thread.

Another object of my invention are printing and coating compositions of the class described for use in making pressure sensitive adhesive tape.

Another object of my invention are printing and coating compositions of the class described for use in making one-time carbon paper.

Another object of my invention are electrically conductive printing and coating compositions of the class described.

Another object of my invention are magnetic printing and coating compositions of the class described.

Another object of my invention are printing and coating compositions of the class described for use on metal foils.

Still another object of my invention are printing and coatingcompositions of the class described for printing on cellulose acetate and Mylar polyester films.

Certain other objects of the invention, will in part, be obvious and will, in part, appear hereinafter.

For a more complete understanding of the nature and scope of my invention, reference may now be had to the following detailed description thereof, wherein illustrative examples and embodiments are set forth.

An ink composition suitable for dissolving in a chlorinated or chlorinated-fluorinated solvent to make a bath to be used in practicing the process and using the apparatus disclosed in my Patent No. 3,067,056 to print on polyethylene film is set forth in the following example:

Example 1 Parts by wt. Chlorinated rubber (67% chlorine) 7.00 Butadiene-acrylonitril copolymer (Paracril C) 7.00 Methyl abietate (Abalyn, Hercules) 4.65 Diallyl phthalate 4.6-5

2, 2'-methylenebis 4-methyl-6-tert-butylp'henol) Antioxidant 2246, American Cyanamid 0.07

Toluidene Red (pigment) 11.60

The ink formulation of Example 1 may be varied in several respects.

While the chlorinated rubber and butadieneacrylonitril copolymer is a preferred resin combination, either of these may be used alone and other synthetic rubber polymers and copolymers and resins soluble in chlorinated or chlorinated-fluorinated solvents may be employed, e.g., styrene-isobutylene copolymer. Likewise, methyl abietate and diallyl phthalate is a preferred plasticizer combination, but other compatible plasticizers may be used. Other antioxidants for protection against heat or actinic light may also be used as well as other pigments. Also dyes which are soluble in chlorinated or chlorinated-fluorinated solvents may be used in place of pigments, if desired.

Another ink formulation which is particularly adapted for printing on polyethylene is the following:

Example 2 Parts by wt. Nylon scrap (thread) 70 Cresylic acid 30 Hansa Yellow (yellow pigment) Example 3 Parts by wt. Chlorosulfonated polymer of ethylene (Hypalon S2) 8O Phenolic-maleic acid ester resin (Super Beckacite 1001, Reichhold) 20 Chlorinated biphenyl (Aroclor) 20 The following is a suitable formulation for an adhesive composition for manufacturing pressure sensitive adhesive tape:

Example 4 Parts by wt. Methyl abietate Alpha-methylstyrene polymer (Dow Resin 276-V2) 15 Hydrogenated rosin (Staybelite Ester 10, Hercules) 15 Chlorinated rubber (6 7% chlorine) 15 2, 2-methylenebis (4-methyl- 6 -te rtiarybutylphenol), heat and light stabilizer 2 Sixty-two parts of this formulation are dissolved in 38 parts of trichloroethylene to prepare a bath suitable for use in the apparatus disclosed in my Patent No. 3,067,056 for applying a pressure sensitive adhesive coating to one side of a traveling web of plastic film such as cellophane, cellulose acetate, polyethylene or Saran. The same formulation may also be applied to advantage to a web of plastic, non-woven fabric, glass fabrics, textile fabrics or paper.

A suitable carbon ink formulation for making onetime carbon paper in the apparatus disclosed in my Patent No. 3,067,056- is shown in the following example:

Parts by wt. Carbon black 1 Alizarine blue 1 2,2-methylenebis (4methyl-6-tertiarybutylphenol) 1 This formulation can be ball milled or milled in a colloid mill and 68 parts of the ink can be dissolved in 32 parts of trichloroethylene to make up a printing or coating bath.

The following formulation is specially adapted for application to a web or sheet for depositing thereon an electrically conductive coating:

Example 6 Parts by wt. Acetylene carbon black 25 Chlorinated parafiin 20 Methyl abietate 20 Lithium nitrate (or lithium chloride) 10 Seventy-five parts of this ink composition may be dissolved in 25 parts of chlorinated solvent to prepare a fountain bath which may be applied in accordance with the method of operation, and by the apparatus, disclosed in Patent No. 3,067,056 to provide printed circuits, printed dry cells and various electrical circuitry.

The following is an example of a magnetic coating composition which may be applied to paper or other sheet material:

Example 7 Parts by wt. Carbonyl iron powder (or any iron oxide powder) 25 Chlorinated paraflin 25 Methyl abietate 25 Seventy-five parts of this formulation may be dissolved in 25 parts of chlorinated solvent and used as the fountain bath in the apparatus disclosed in Patent No. 3,067,- 056. After application to a sheet or web the resulting coating may be magnetized.

The following formulation is particularly suitable for use in printing metal foil (e.g. aluminum foil) by the process and apparatus described in Patent No. 3,067,056.

Example 8 Parts by wt. Ethyl cellulose (low viscosity) 20 Alpha-methylstyrene polymer (Dow Resin 276-V2) 10 Methyl abietate 10 A20 oil blue B 5 Forty-five parts of this formulation are dissolved in 55 parts of trichloroethylene or other chlorinated solvent and used as the fountain solution in the apparatus.

The following ink composition in chlorinated solvent is particularly adapted for printing on films of cellulose acetate and Mylar polyester films:

Example 9 Parts by wt. Ethylene dichloride 45 Methyl methacrylate (Plexiglas) 45 Glacial acetic acid 10 TiO pigment 10 Chlorinated or chlorinated-fluorinated solvents are used in this process for a number of reasons. They vaporize readily at temperatures between about 75 F. to F. into vapors which are much heavier than air so as to settle into the bottom of the condenser units. These vapors condense easily and if desired for use in other formulations may be readily reclaimed by distilling and condensing. Chlorinated or halogenated solvents are in the nature of dry solvents which do not wet or hydrate the webs even if the web happens to be a highly porous and absorptive material, or a highly hydrogen bonded material, such as newsprint. When these chlorinated solvents are heated to the temperatures used in this invention, they have very high dissolving or suspending capacities for materials used in the ink or coating compositions including resins, fillers and pigments. Such materials dissolve or disperse readily in chlorinated solvents to a much higher or greater extent than they can be dissolved or dispersed in ordinary solvents. This high solubility and dispersibility is due to the combined solvent power and the heat. In practice, resins, fillers and pigments and other materials which are used in the inks or coating composition to be applied in accordance with the present invention are milled in the heated phase into or in the presence of hot chlorinated solvent. By following this procedure, it is possible to easily provide inks or coating compositions which contain up to as much as 50 to 60% solids. In the usual cold ink or coating compositions the solids content usually does not exceed 20% by weight.

Chlorinated and chlorinated-fluorinated solvents are non-polar and by the incorporation therein of various known anti-static chemicals or agents having anionic or cationic properties, they will serve to change or convert the polarity of a web such as newsprint from a negative charge to a positive charge while being printed or coated in accordance with this invention. The following antistatic chemicals or agents may be used:

(a) Arquad S2C50 Armour Chemical Co. (soya trimethyl ammonium chloride 50% and dimethyl dicocoammonium chloride 50%) (b) Rosin amine D (dehydroabietylamine N-acetamide) (c) Cetyltrimethyl ammonium bromide (d) Cetyl pyridinium chloride (e) Lauryl pyridinium chloride (f) N-butylamine lactate N,N-butyl lactamide (g) Sapamine K.W.C. Ciba Co. (tertiary ammonium compound) (h) Dilauryl dipropyl ammonium bromide (i) n-Soya-n-ethyl morpholinum ethosulfate (j) Polyoxyalkylene stearate (Atlas Powder Co. G-33- This conversion or change in electrical charge is facilitated by having the impression roll formed of Thiokol, Teflon, or silicone rubber materials which are loaded with acetylene black and/or graphite or molybdenum disulphide. By employing anti-static chemicals or agents in the chlorinated solvents and by also forming the impression roll of one of the anti-friction materials mentioned above, it is possible to eliminate or substantially prevent the wicking action normally associated with a pressure printing operation such as is involved in a rotogravure or rotogravure printing unit.

In view of the teaching contained in the foregoing examples, those skilled in the art will be able to make and use either the compositions specifically disclosed herein or such modified formulations as may be required for their needs without departing from the spirit and scope of the present invention.

I claim:

1. A carbon ink composition having substantially the following composition:

Parts by wt. Armid O 30 Stearamide "percent" 6 Oleamide do 91 Linoleamide do 3 Sugar Cane Wax 30 Chlorinated parafiin 5 Carbon black 1 Alizarine blue l 2,2'-methylenebis(4-n1ethyl-6-tertiary-butylphenol 1 References Cited UNITED STATES PATENTS 2,236,602 4/1941 Neidich 10623 X 2,647,060 7/1953 Armstrong 10626 ALEXANDER H. BRODMERKEL, Primary Examiner.

I. B. EVANS, Assistant Examiner. 

